Gold nanoparticles stabilized by modified halloysite nanotubes for catalytic applications

A highly sustainable prototype of a flow system based on gold nanoparticles (4.2 nm) supported on thiol‐functionalized halloysite nanotubes (HNTs) was developed for catalytic applications. The catalytic performances were evaluated using the reduction of 4‐nitrophenol to 4‐aminophenol as a model system. Under the best experimental conditions (0.0001 mol%, 1.97 × 10^?8 mg of Au nanoparticles), an impressive apparent turnover frequency value up to 2 204 530 h^?1 was achieved and the halloysite‐based catalyst showed full recyclability even after ten cycles. The high catalytic activity confirms the importance of the use of HNTs as support for Au nanoparticles that can exert a synergistic effect both as medium for transfer of electrons from borohydride ions to 4‐nitrophenol and by modulating interfacial electron transfer dynamics. With the application of flow technology, the obtained heterogeneous HNT@Au catalyst was fully recovered and reused for at least one month.     

Non-woven cotton fabric based intimately coupling of photocatalysis and biodegradation system for efficient removal of Cu(II) complex in water

The efficient remediation of heavy metal complexes in water has become a difficult and challenging task owing to their high stability and strong mobility. In this study, a novel strategy was employed for highly efficient removal of Cu-citrate by using intimately coupled photocatalysis and biodegradation (ICPB) system with non-woven cotton fabric as a carrier. Experimental results showed that the ICPB system caused 94% Cu removal, which was higher than those of single photocatalysis. After 5 cycles, Cu removal efficiency could still reach 78% within 5 h. The existence of 0–40 mg/L citrate had negligible influence, whereas the presence of 60–100 mg/L citrate exhibited a limited adverse effect on Cu removal (～70%). The decomplexation of Cu-citrate was realized via the function of free radicals and microorganisms. Two main processes, such as bio-adsorption of Cu²⁺ by microorganisms, deposition of Cu⁰ on the surface of material, played important role in Cu removal from aqueous solution. The dominant microorganisms in the system were Proteobacteria, Actinobacteria, Bacteroidetes, Chloroflexi, Chlorophyta, Planctomycetes, and Verrucomicrobia. Furthermore, the performance of ICPB system was also validated through treatment of other heavy metal complexes. This study provided a feasible strategy for the decontamination of heavy metal complexes in wastewater.     

Assessment of natural radioactivity in soil samples and comparison of direct and indirect measurement of environmental air kerma rate

This study presents the high purity germanium (HPGe) gamma spectrometric measurement of natural radioactivity mainly due to ²²⁶Ra, ²³²Th and ⁴⁰K in soil samples collected in Ferozepur and Faridkot district of Punjab, India. ²²⁶Ra activity varied from 28.6 to 51.1 Bq kg⁻¹ with the mean of 39.7 Bq kg⁻¹. The range and mean activity of ²³²Th were 42.9–73.2 and 58.2 Bq kg⁻¹, respectively. ⁴⁰K activity was in the range of 470.9–754.9 Bq kg⁻¹ with the mean of 595.2 Bq kg⁻¹. The air kerma rate (AKR) at 1 m height from the ground was also measured using gamma survey meter in all the sampling locations, which was ranging from 92.1 to 122.8 nGy h⁻¹ with the mean of 110.6 nGy h⁻¹. The radiological parameters such as Ra_eq and activity index of the soil samples were also evaluated, which are the tools to assess the external radiation hazard due to building materials. The mean and range of the Ra_eq values were 168.7 and 132.9–210.4 Bq kg⁻¹, respectively, whereas the activity index varied from 0.5 to 0.8 with the mean value of 0.62. These indices show that the indoor external dose due to natural radioactivity in the soil used for the construction will not exceed the dose criteria. The AKR was also evaluated from soil activity concentration and altitude correction of cosmic radiation contribution. The statistical tests such as Pearson correlation, spearman rank correlation, box and whisker plot, the Wilcoxon/Mann–Whitney test and chi-square test, were used to compare the measured AKR with evaluated AKR, which indicates good correlation.     

Application of response surface methodology to optimize pipette tip micro-solid phase extraction of dyes from seawater by molecularly imprinted polymer and their determination by HPLC

In this paper, a novel pipette tip micro-solid phase extraction based on molecularly imprinted polymer as a selective sorbent was developed and applied for extraction, pre-concentration and high-performance liquid chromatographic determination of trace amounts of malachite green (MG), rhodamine B (RB), methyl orange (MO) and acid red 18 (AR) dyes in seawater samples. Different parameters affecting the extraction efficiency such as type and volume of eluent solvent, sample volume, number of cycles of extraction and desorption, amount of sorbent and pH of the sample solution were evaluated using one-variable-at-a-time and response surface methodology. In order to optimize dyes extraction, seven factors in three levels were used for Box–Behnken experimental design. Under optimum extraction condition, pH of sample solution was 3.1 for MG, 3.0 for RB, 7.1 for MO and 6.1 for AR; volume of eluent solvent (HCl, 0.5 mol L⁻¹) was 200 µL; volume of the sample solution was 10 mL (for MG) and 4 mL (for RB, MO and AR); the concentration of triton X-114 was 0.085 (MG), 0.10 (RB), 0.08 (MO) and 0.075 (AR) % v/v; the number of extraction cycles was 10 (MG), 6 (RB), 5 (MO) and 7 (AR); the number of elution cycles was 10, 6, 5 and 9, respectively, for MG, RB, MO and AR; NaCl concentration was 0.4 mol L⁻¹; and amount of MIP was 2.0 mg for all dyes. The linear range of calibration curves was 0.5–250.0 µg L⁻¹ for malachite green and methyl orange and 0.5–150.0 µg L⁻¹ for both rhodamine B and acid red 18. The detection limits calculated to be 0.083, 0.10, 0.12 and 0.17 µg L⁻¹ for MG, RB, MO and AR, respectively. The developed protocol was successfully used for determination of dyes in seawater of Chabahar Bay. The mean recoveries were ranged between 76.1 and 97.3% by mean relative standard deviations of 1.2–7.1%.

     

Preparation and electrochemical characterization of the porous sulfur cathode using a gelatin binder

A novel porous sulfur cathode in which a gelatin was used as the binder was prepared by using a freeze–drying method at −58 °C. The porous structure provides channels for electrolyte infiltration and then facilitates ion diffusion. This porous sulfur cathode has a high initial capacity of 1235 mAh g⁻¹ and a high reversible capacity of 626 mAh g⁻¹ after 50 cycles, both of which are higher than that of the normal cathodes with compact structures.     

Electrochemical performance of sulfur composite cathode materials for rechargeable lithium batteries

The structure and characteristic of carbon materials have a direct influence on the electrochemical performance of sulfur-carbon composite electrode materials for lithium-sulfur battery.In this paper,sulfur composite has been synthesized by heating a mixture of elemental sulfur and activated carbon,which is characterized as high specific surface area and microporous structure.The composite,contained 70%sulfur,as cathode in a lithium cell based on organic liquid electrolyte was tested at room temperature....     

Sequential spectrofluorimetric determination of free and total glycerol in biodiesel in a multicommuted flow system

A new procedure for spectrofluorimetric determination of free and total glycerol in biodiesel samples is presented. It is based on the oxidation of glycerol by periodate, forming formaldehyde, which reacts with acetylacetone, producing the luminescent 3,5-diacetyl-1,4-dihydrolutidine. A flow system with solenoid micro-pumps is proposed for solution handling. Free glycerol was extracted off-line from biodiesel samples with water, and total glycerol was converted to free glycerol by saponification with sodium ethylate under sonication. For free glycerol, a linear response was observed from 5 to 70 mg L⁻¹ with a detection limit of 0.5 mg L⁻¹, which corresponds to 2 mg kg⁻¹ in biodiesel. The coefficient of variation was 0.9% (20 mg L⁻¹, n = 10). For total glycerol, samples were diluted on-line, and the linear response range was 25 to 300 mg L⁻¹. The detection limit was 1.4 mg L⁻¹ (2.8 mg kg⁻¹ in biodiesel) with a coefficient of variation of 1.4% (200 mg L⁻¹, n = 10). The sampling rate was ca. 35 samples h⁻¹ and the procedure was applied to determination of free and total glycerol in biodiesel samples from soybean, cottonseed, and castor beans.     

Nanocrystalline ZnMn2O4 as a novel lithium-storage material

Nanocrystalline ZnMn₂O₄ is prepared by a polymer-pyrolysis route and used as a novel anode for lithium ion batteries. XRD and HRTEM studies reveal that the products are highly phase-pure and 30–60 nm in size. Galvanostatic cycling of ZnMn₂O₄ electrode at 100 mA g⁻¹ (about 0.52 mA cm⁻²) between 0.01 and 3.0 V up to 50 cycles exhibits almost stable cycling performance between 10 and 50 cycles with only an average capacity fade of 0.20% per cycle and the electrode still maintains a capacity of 569 mAh g⁻¹ after 50 cycles.     

The 1H and 13C NMR chemical shifts of Strychnos alkaloids revisited at the DFT level

The density functional theory calculation of ¹H and ¹³C NMR chemical shifts in a series of ten 10 classically known Strychnos alkaloids with a strychnine skeleton was performed at the PBE0/pcSseg-2//pcseg-2 level. It was found that calculated ¹H and ¹³C NMR chemical shifts provided a markedly good correlation with experiment characterized by a mean absolute error of 0.08 ppm in the range of 7 ppm for protons and 1.67 ppm in the range of 150 ppm for carbons, so that a mean absolute percentage error was as small as ~1% in both cases.     

Bimetallic CoNiSe2/C nanosphere anodes derived from Ni-Co-metal-organic framework precursor towards higher lithium storage capacity

Through uncomplicated carbonation process, a carbon-embedded CoNiSe₂/C nanosphere was synthesized from Ni-Co-MOF (metal-organic framework) precursor whose controllable structure and synergistic effect of bimetallic Ni/Co brought CoNiSe₂/C anodes with high specific surface area (172.79 m²/g) and outstanding electrochemical performance. CoNiSe₂/C anodes obtained reversible discharge capacities of 850.9 mAh/g at 0.1 A/g after cycling for 100 cycles. In addition, CoNiSe₂/C exhibits excellent cycle stability and reversibility in the rate test at a current density of 0.1–2.0 A/g. When the current density returns to 0.5 A/g for 150 cycles, its discharge ratio the capacity is 330.8 mAh/g. Electrochemical impedance spectroscopy (EIS) tests suggested that CoNiSe₂/C anodes had a lower charge transfer impedance of 130.02 Ω after 30 cycles. In-situ X-ray diffraction (XRD) tests confirmed the alloying mechanism of CoNiSe₂/C which realized higher lithium storage capacity. This work affords substantial evidence for the extension of bimetallic selenides in secondary batteries, promoting the development of bimetallic selenides in anode materials for LIBs.     

Facile synthesis of Ti4+‐immobilized affinity silica nanoparticles for the highly selective enrichment of intact phosphoproteins

Currently, great challenges to top‐down phosphoproteomics lie in the selective enrichment of intact phosphoproteins from complex biological samples. Herein, we developed a facile approach for synthesis of Ti⁴⁺‐immobilized affinity silica nanoparticles and applied them to the selective separation and enrichment of intact phosphoproteins based upon the principle of metal(IV) phosphate/phosphonate chemistry. The as‐prepared affinity materials exhibited high selectivity and adsorption capacities for model phosphoproteins (328.9 mg/g for β‐casein, 280.5 mg/g for ovalbumin, and 225.8 mg/g for α‐casein), compared with nonphosphoproteins (79.28 mg/g for horseradish peroxidase, 72.70 mg/g for BSA, and 27.28 mg/g for lysozyme). In addition, the resuability of the affinity silica nanoparticles was evaluated, and the results demonstrated a less than 10% loss of adsorption capacity after six adsorption–regeneration cycles. The practicability of the affinity materials was demonstrated by separating phosphoproteins from protein mixtures and drinking milk samples, and the satisfactory results indicated its potential in phosphoproteomics analysis.     

Enhancement of Cd2+ removal on CuMgAl-layered double hydroxide/montmorillonite nanocomposite: Kinetic,isotherm, and thermodynamic studies

In recent decades, great progress has been made in the application of adsorption processes to mitigate water pollution by hazardous metals. However, developing a highly efficient adsorbent is essential if the adsorption process is to be successfully applied in practical applications. In this study, a CuMgAl-layered double hydroxides/montmorillonite nanocomposite (CuMgAl-LDH/MMt) was prepared, characterized, and then used as a novel adsorbent for adsorption of Cd²⁺ ions from wastewater. The effects of initial pH, adsorbent dosage, agitation speed, particle size, contact time, initial Cd²⁺ concentration, and temperature on the pollutant removal efficiency were analyzed. An isotherm model reading revealed that the results of the experimental work were a good fit with the Freundlich model. The maximum adsorption capacity was reached at 174.87 mg/g under optimal conditions (pH 5, dosage of 0.02 g/l, agitation speed of 150 rpm, and particle size of 87 μm) at 50 ppm after 120 min of adsorption time. Kinetic studies showed that pseudo-second-order models were best fitted to the adsorption data, indicating heterogeneous adsorption of Cd²⁺ ions onto multilayer CuMgAl-LDH/MMt sites, and that the adsorption process is primarily chemical adsorption. Thermodynamic parameters (ΔS^o, ΔH^o, and ΔG^o) demonstrated that Cd²⁺ adsorption onto adsorbent was exothermic and spontaneous. Moreover, the synthesized adsorbent can be recovered after five consecutive cycles with a minimal reduction in the adsorption ability of 29.56 %. The study showed that specific heavy metals can be removed from aqueous solution by a newly prepared adsorbent due to its excellent morphology, high stability under a wide range of conditions, recyclability, and high adsorption capacity.     

Inclusion of W in electroless Ni–B coating developed from a stabilizer free bath and investigation of its tribological behaviour

In the present study, tribological and corrosion behaviour of electroless Ni–B–W (ENB-W) coatings prepared from stabilizer-free baths and deposited on AISI 1040 steel substrates were examined. Three distinct coating bath temperatures (85 °C, 90 °C, and 95 °C) were varied for coating deposition. The coatings showed nodular morphology. Thermogravimetric study of ENB-W coatings revealed improved thermal stability attained at 95 °C bath temperature. The microhardness of ENB-W coating was 645, 690, and 720 HV₁₀₀ at bath temperatures of 85 °C, 90 °C, and 95 °C respectively. The inclusion of W to Ni–B coating enhanced the hardness by ∼150 HV₁₀₀. On a pin-on-disc tribometer, wear test was conducted. The precipitation of Ni (111) and its borides occurred post sliding wear at high temperatures (300 °C). Ni (111) crystallite size decreased because of high temperature sliding wear at 300 °C with an increase in coating bath temperature. With a reduction in crystallite size at high temperatures, both wear rate and COF decreases. The scratch hardness and first critical load of failure of the coatings was determined using a scratch tester. Using potentiodynamic polarization, corrosion resistance of ENB-W coatings in 3.5% NaCl was investigated. ENB-W coatings could provide shielding to AISI 1040 steel from corrosion. Though the corrosion resistance is poor with respect to lead stabilized coatings.     

Carbon fibers modified with carbon nanoparticles by a facile and fast flame preparation for in-tube solid-phase microextraction

Carbon fibers (CFs) were modified with carbon nanoparticles (CNPs) by a facile and fast flame preparation method. CNPs-CFs were observed by scanning electron microscope, and the nano-scaled granular structure on the surface was found. This material was also characterized by Raman microscope and X-ray photoelectron spectroscope. It was placed into a polyetheretherketone tube to get an extraction tube, which was connected with high performance liquid chromatography for online analysis. The tube displayed the effective extraction to several polycyclic aromatic hydrocarbons (PAHs), based on the possible hydrophobic and π stacking mechanism. Under the optimized conditions (60 mL of sample volume, 2.00 mL min^?1 of sample rate, 0.5% of methanol in sample, 2.0 min of desorption time), an analytical method towards these PAH targets was established. The low limits of detection (0.001–0.005 μg L^?1), satisfactory linear ranges (0.003–5.0 μg L^?1, 0.003–10.0 μg L^?1) and efficient enrichment factors (1012–3164) were presented. The method was applied to detect trace targets in several water samples and satisfactory results were obtained. The method provided some superiorities over other analytical methods, like online test, shorter time and better sensitivity.     

Facile synthesis of magnetic hybrid metal–organic frameworks with high adsorption capacity for methylene blue

A magnetic hybrid material (Fe₃O₄‐COOH/HKUST‐1) was easily synthesized via a two‐step simple solvothermal method. Through adding sodium acrylate directly into the synthesis of Fe₃O₄ spheres, the surface has more carboxyl groups. It is notable that the reactions proceed without use of organic surfactants. The magnetic hybrid material was characterized using various techniques. The magnetic hybrid material has a high specific surface area (430.15 m² g⁻¹) and excellent magnetism (23.65 emu g⁻¹). It is an efficient adsorbent for removing organic dyes like methylene blue (MB) from aqueous solution. It also can be easily recovered from liquid media using an external magnetic field. Adsorption experiment shows the magnetic hybrid material possesses a high adsorption capacity (118.6 mg g⁻¹), and has high adsorption efficiency (94.3%) after five adsorption cycles with ethanol (0.2% HCl) as eluent. The sorption kinetics and isotherm analysis indicate these sorption processes are better fitted to the pseudo‐second‐order and Langmuir equations. Thermodynamic study shows the sorption processes are spontaneous and endothermic.     

Multi-length scale wear damage mechanisms of ultra-high molecular weight polyethylene nanocomposites

Ultra-high molecular weight polyethylene (UHMWPE) is reinforced with 1–3 wt % sliver (Ag) nanoparticles and zinc oxide (ZnO) micro-rods, and tensile strength as well as wear resistance of the samples is evaluated. Tensile strength was observed to increase with Ag and ZnO reinforcement up to 18% for 1 wt % ZnO and 1 wt % Ag, but in case of 3 wt % ZnO and 3 wt % Ag + 3 wt % ZnO, it decreases marginally by 4% when compared with neat polymer. The sliding wear rate for 1 wt % Ag + 1 wt % ZnO and 3 wt % Ag + 3 wt % ZnO decreases from 9.54 × 10⁻⁵ mm³ (neat polymer) to 7.49 × 10⁻⁵ mm³ and 5.65 × 10⁻⁵mm³, respectively, showing the synergistic effect of Ag and ZnO reinforcement. In scratch testing, minimum damage is obtained in 1 wt % ZnO reinforced polymer. On one hand, where micro-scratch damage is resisted by harder ZnO, whereas on the other hand, pin on disc wear (repeated surface damage) is protected by softer Ag tribolayer. The improved tensile strength (up to 9.7%) and wear resistance with synergistic addition of Ag and ZnO (both 1 wt %) opens a window in the development of bearing surface biomaterials providing improved longevity and durability, thus, may reduce the chances of revision surgery.     

The Effects of Gas Composition on Active Species and Byproducts Formation in Gas–Water Gliding Arc Discharge

The effects of gas composition on hybrid gas–water gliding arc discharge plasma reactor have been studied. The voltage cycles are characterized by a moderate increase in the tension which is represented by a peak followed by an abrupt decrease and a current peak in the half period (10 ms). Emission spectrum measurements revealed that ^•OH hydroxyl radicals are present in the discharge with feeding any gas. The H₂O₂ concentrations reach 38.0, 15.0, 10.0, and 8.0 mg/l after 25 min plasma treatment with oxygen, argon, air, and nitrogen, respectively. O₃ was produced when oxygen and air are used, but not when nitrogen and argon. The O₃ concentration reached the highest value 1.0 mg/l after 25 min plasma treatment with oxygen feeding gas, but gradually decreased to 0.2 mg/l after that. With feeding nitrogenous gas, NO₂ ⁻ and NO₃ ⁻ byproducts were formed by the plasma chemical process.     

Experimental design,machine learning approaches for the optimization and modeling of caffeine adsorption

In the current research, the sorption of caffeine on fresh and calcined Cu–Al layered double hydroxide was comparatively studied based on adsorption parameters, adsorption kinetics, and adsorption isotherm. Response surface methodology (RSM), support vector machine (SVM) and artificial neural network (ANN), as data mining methods, were applied to develop models by considering various operating variables. Different characterization methods were exploited to conduct a comprehensive analysis of the characteristics of HDL in order to acquire a thorough understanding of its structural and functional features. The Langmuir model was employed to accurately describe the maximum monolayer adsorption capacity for calcined sample (q_max) of 152.99 mg/g mg/g with R² = 0.9977. The pseudo-second order model precisely described the adsorption phenomenon (R² = 0.999). The thermodynamic analysis also reveals a favorable and spontaneous process. The ANN model predicts adsorption efficiency result with R² = 0.989. The five-fold cross-validation was achieved to evaluate the validity of the SVM. The predication results revealed approximately 99.9% accuracy for test datasets and 99.63% accuracy for experiment data. Moreover, ANOVA analysis employing the central composite design-response surface methodology (CCD-RSM) indicated a good agreement between the quadratic equation predictions and the experimental data, which results in R² of 0.9868 and the highest removal percentages in optimized step were obtained for RSM (pH 5.05, mass of adsorbent 20 mg, time of 72 min, and caffeine concentrations of 22 mg/L). On the whole, the findings confirm that the proposed machine learning models provided reliable and robust computer methods for monitoring and simulating the adsorption of pollutants from aqueous solutions by Cu–Al–LDH.     

An acidic cellulose–chitin hybrid gel as novel electrolyte for an electric double layer capacitor

A novel acidic cellulose–chitin hybrid gel electrolyte including binary ionic liquids (ILs) with an aqueous H₂SO₄ solution was prepared for an electric double layer capacitor (EDLC). Its electrochemical characteristics were investigated by galvanostatic charge–discharge measurements. The test cell with a hybrid gel electrolyte shows a specific capacitance of 162 F g^?1 at room temperature, which is higher than that for a cell with an H₂SO₄ electrolyte, 155 F g^?1. This hybrid gel electrolyte exhibits excellent high-rate discharge capability in a wide range of current densities as well as an aqueous H₂SO₄ solution. The discharge capacitance of the test cell can retain over 80% of its initial value in 100,000 cycles even at a high current density of 5000 mA g^?1.     

Minimization of mass interferences in quadrupole inductively coupled plasma mass spectrometric (ICP-MS) determination of palladium using a flow injection on-line displacement solid-phase extraction protocol

A flow injection on-line displacement solid-phase extraction protocol was employed to minimize mass interferences with determination of palladium by inductively coupled plasma mass spectrometry (ICP-MS). The developed method involved in on-line complexing of Ag⁺ with pyrrolidine dithiocarbamate (PDC), presorption of the resultant Ag–PDC onto a microcolumn packed with the cigarette filter, displacement sorption of Pd²⁺ through loading the sample solution onto the microcolumn due to on-line displacement reaction between Pd²⁺ and the presorbed Ag–PDC, elution of the retained Pd²⁺ with 50 μL of ethanol for on-line ICP-MS detection. Interferences from co-existing heavy metal ions with lower stability of their PDC complexes relative to Ag–PDC were minimized/eliminated. No interferences from 5 mg L^− 1 Zn and 3 mg L^− 1 Pb for ¹⁰⁴Pd, 0.4 mg L^− 1 Cu for ¹⁰⁵Pd, 6 mg L^− 1 Zn and 2 mg L^− 1 Cd for ¹⁰⁶Pd, 6 mg L^− 1 Zn and 3 mg L^− 1 Cd for ¹⁰⁸Pd, and 2 mg L^− 1 Cd for ¹¹⁰Pd were observed for the determination of 100 ng L^− 1 Pd. The enhancement factors of 71–75, sample throughput of 23 samples h^− 1 and detection limits of 2.8–3.5 ng L^− 1 were achieved with the consumption of 3.0 mL of sample solution. The precision (RSD) for eleven replicate determinations of Pd at the 100 ng L^− 1 level was 1.8–2.7%. The developed method was applied to the determination of palladium in rock samples.